KR20230097070A - Composition and preparation for hafnium carbide ceramic precursors - Google Patents
Composition and preparation for hafnium carbide ceramic precursors Download PDFInfo
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- KR20230097070A KR20230097070A KR1020237016773A KR20237016773A KR20230097070A KR 20230097070 A KR20230097070 A KR 20230097070A KR 1020237016773 A KR1020237016773 A KR 1020237016773A KR 20237016773 A KR20237016773 A KR 20237016773A KR 20230097070 A KR20230097070 A KR 20230097070A
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- Prior art keywords
- hafnium
- polymer composition
- precursor polymer
- ceramic precursor
- cyclopentadienyl
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- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 239000012700 ceramic precursor Substances 0.000 title claims description 34
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 title claims description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000000919 ceramic Substances 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 10
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 claims abstract description 7
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 64
- 229910052735 hafnium Inorganic materials 0.000 claims description 26
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 18
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 14
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 12
- CBKDTJXMXIYANY-UHFFFAOYSA-N cyclopentane;hafnium Chemical compound [Hf].[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 CBKDTJXMXIYANY-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- MXVFWIHIMKGTFU-UHFFFAOYSA-N C1=CC=CC1[Hf] Chemical compound C1=CC=CC1[Hf] MXVFWIHIMKGTFU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 239000007818 Grignard reagent Substances 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- IZYHZMFAUFITLK-UHFFFAOYSA-N 1-ethenyl-2,4-difluorobenzene Chemical compound FC1=CC=C(C=C)C(F)=C1 IZYHZMFAUFITLK-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 239000011215 ultra-high-temperature ceramic Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920005588 metal-containing polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GJEONJVNTMLKMR-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].[Hf+3] Chemical compound [Cl-].[Cl-].[Cl-].[Hf+3] GJEONJVNTMLKMR-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- -1 cyclopentadienyl anions Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- UFSCUAXLTRFIDC-UHFFFAOYSA-N oxalosuccinic acid Chemical compound OC(=O)CC(C(O)=O)C(=O)C(O)=O UFSCUAXLTRFIDC-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
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Abstract
폴리(카르보하프노센) 조성물 및 관련 폴리(카르보메탈로센) 조성물 뿐만 아니라, 염화하프늄 및 2-부틴-1,4-디올의 반응으로부터 형성된 조성물을 포함한, 고온 금속 탄화물 세라믹의 제조에 유용한 금속 함유 중합체 조성물이 기재되어 있다. 그러한 조성물의 합성 방법이 제공된다.Useful in the manufacture of high-temperature metal carbide ceramics, including poly(carbohafnocene) compositions and related poly(carbometallocene) compositions, as well as compositions formed from the reaction of hafnium chloride and 2-butyne-1,4-diol. Metal-containing polymeric compositions are described. Methods of synthesizing such compositions are provided.
Description
관련 related 출원에 대한 교차 참조Cross reference to application
본원은 2020년 10월 30일자로 출원된 미국 특허 가출원 제63/107,615호의 이득을 청구하며, 그의 개시내용은 본원에 참조로 그 전문이 포함된다.This application claims the benefit of US Provisional Patent Application No. 63/107,615, filed on October 30, 2020, the disclosure of which is incorporated herein by reference in its entirety.
기술 분야technical field
본 발명은 금속 탄화물 세라믹의 제조에 유용한 폴리(카르보메탈로센) 중합체 및 하프늄 함유 2-부틴-1,4-디올 중합체를 포함한 선형 및 분지형 중합체의 조성물 및 그의 합성 방법, 구체적으로 초고온 탄화하프늄(HfC) 세라믹의 합성을 위하여 구성된 폴리(카르보하프노센) 중합체 및 하프늄 함유 2-부틴-1,4-디올 중합체에 관한 것이다.The present invention relates to compositions of linear and branched polymers, including poly(carbometallocene) polymers and hafnium-containing 2-butyne-1,4-diol polymers useful for the production of metal carbide ceramics, and methods for their synthesis, specifically ultrahigh temperature carbonization. Poly(carbohalofnocene) polymers and hafnium-containing 2-butyne-1,4-diol polymers constructed for the synthesis of hafnium (HfC) ceramics.
탄화하프늄(HfC)은 초고온 세라믹(UHTC) 중에서 가장 높은 융점을 지녀서 극초음속 자동차 부품에 특히 유용하게 된다. 이오네스쿠(Ionescu) 및 동료들이 최근 리뷰 논문에서 요약한 바와 같이 HfC 제조에 대한 흥미로운 접근법은 중합체 HfC 전구체의 고온 전환을 수반한다(E. Ionescu et al., Polymer-Derived Ultra-High Temperature Ceramics (UHTCs) and Related Materials, Adv . Eng . Mat., 21, 1900269 (2019)). 그러나, 이오네스쿠가 보고한 예비-세라믹 중합체는 너무 많은 유리 탄소를 갖거나 또는 용매 중에서 불용성이거나 또는 합성을 위한 리튬 시약을 필요로 한다. 특허 출원 CN104016679A에는 타르타르산, 옥살로숙신산 및 시트르산을 사용한 수계 HfC 전구체가 보고되어 있다. 그러나, 이들 중합체는 너무 많은 산소를 함유하여 유용하지 않다. 그러한 접근법의 경우, 생성된 중합체는 낮은 세라믹 수율 또는 불량한 가공력을 갖거나 또는 단순히 너무 고가이다.Hafnium carbide (HfC) has the highest melting point among ultrahigh temperature ceramics (UHTC), making it particularly useful for hypersonic vehicle parts. As summarized in a recent review paper by Ionescu and colleagues, an interesting approach to HfC fabrication involves high-temperature conversion of polymeric HfC precursors (E. Ionescu et al., Polymer-Derived Ultra-High Temperature Ceramics (UHTCs) ) and Related Materials, Adv . Eng . Mat. , 21, 1900269 (2019)). However, the pre-ceramic polymers reported by Ionescu either have too much free carbon or are insoluble in solvents or require lithium reagents for synthesis. Patent application CN104016679A reports an aqueous HfC precursor using tartaric acid, oxalosuccinic acid and citric acid. However, these polymers contain too much oxygen to be useful. For such approaches, the resulting polymers have low ceramic yields or poor processability or are simply too expensive.
본 발명의 한 실시양태에 의하면, 하기로부터 선택된 적어도 1종의 폴리(카르보메탈로센)을 포함하는 세라믹 전구체 중합체 조성물이 개시되어 있다:According to one embodiment of the present invention, a ceramic precursor polymer composition is disclosed comprising at least one poly(carbometallocene) selected from:
상기 식에서, C5H5는 시클로펜타디에닐 리간드이며, n, x 및 y는 0 초과의 정수이며, M은 금속이다. 바람직한 실시양태에서, M은 Hf, Zr, Ti, V, Nb, Ta 및 그의 조합으로부터 선택된 금속이다.In the above formula, C 5 H 5 is a cyclopentadienyl ligand, n, x and y are integers greater than 0, and M is a metal. In a preferred embodiment, M is a metal selected from Hf, Zr, Ti, V, Nb, Ta and combinations thereof.
바람직한 실시양태에서, 세라믹 전구체 조성물은 하기를 포함한다:In a preferred embodiment, the ceramic precursor composition comprises:
바람직한 실시양태에서, 세라믹 전구체 조성물 하기를 포함한다:In a preferred embodiment, the ceramic precursor composition comprises:
일부 실시양태에서, x/y 비는 2 초과이다. 바람직한 실시양태에서, x/y 비는 2 내지 10이다.In some embodiments the x/y ratio is greater than 2. In a preferred embodiment, the x/y ratio is between 2 and 10.
바람직한 실시양태에서, 세라믹 전구체 중합체 조성물은 하기 반응에 의하여 합성된다:In a preferred embodiment, the ceramic precursor polymer composition is synthesized by the following reaction:
상기 식에서, C5H5는 시클로펜타디에닐 리간드이며, X1 및 X2는 할라이드이며, n은 0 초과의 정수이다. 바람직한 실시양태에서, X1 및 X2는 클로라이드 및 브로마이드로 이루어진 군으로부터 별도로 선택된다. 바람직한 실시양태에서, X1 및 X2는 둘 다 클로라이드이다.In the above formula, C 5 H 5 is a cyclopentadienyl ligand, X 1 and X 2 are halides, and n is an integer greater than zero. In a preferred embodiment, X 1 and X 2 are separately selected from the group consisting of chloride and bromide. In a preferred embodiment, X 1 and X 2 are both chloride.
바람직한 실시양태에서, 세라믹 전구체 중합체 조성물은 하기 반응에 의하여 합성된다:In a preferred embodiment, the ceramic precursor polymer composition is synthesized by the following reaction:
상기 식에서, C5H5는 시클로펜타디에닐 리간드이며, X1, X2 및 X3은 클로라이드 및 브로마이드로 이루어진 군으로부터 별도로 선택된 할라이드이며, x 및 y는 0 초과의 정수이다.In the above formula, C 5 H 5 is a cyclopentadienyl ligand, X 1 , X 2 and X 3 are halides separately selected from the group consisting of chloride and bromide, and x and y are integers greater than zero.
바람직한 실시양태에서, 폴리(카르보하프노센) 중합체의 형성 방법은 비스(시클로펜타디에닐)하프늄 디할라이드를 제공하는 단계 및, 비스(시클로펜타디에닐)하프늄 디할라이드를 화학식 XMg(CH2)jMgX의 디-그리나드 시약과 반응시키는 단계를 포함하며, 여기서 X는 할라이드이며, j는 4 또는 5이다. 또 다른 바람직한 실시양태에서, 상기 방법은 모노(시클로펜타디에닐)하프늄 트리할라이드를 제공하는 단계를 추가로 포함하며, 반응은 비스(시클로펜타디에닐)하프늄 디할라이드 및 모노(시클로펜타디에닐)하프늄 트리할라이드의 혼합물을 화학식 XMg(CH2)jMgX의 디-그리나드 시약과 반응시키는 것을 추가로 포함한다. 상기 방법의 바람직한 실시양태에서, 모노(시클로펜타디에닐)하프늄 트리할라이드에 대한 비스(시클로펜타디에닐)하프늄 디할라이드의 비는 2 내지 10이다.In a preferred embodiment, the process for forming the poly(carbohalfnocene) polymer comprises providing a bis(cyclopentadienyl)hafnium dihalide, and the bis(cyclopentadienyl)hafnium dihalide having the formula XMg(CH 2 ) and j reacting MgX with a di-grignard reagent, wherein X is a halide and j is 4 or 5. In another preferred embodiment, the method further comprises providing mono(cyclopentadienyl)hafnium trihalide, wherein the reaction comprises bis(cyclopentadienyl)hafnium dihalide and mono(cyclopentadienyl) further comprising reacting the mixture of hafnium trihalides with a Di-Grinard reagent of formula XMg(CH 2 ) j MgX. In a preferred embodiment of the method, the ratio of bis(cyclopentadienyl)hafnium dihalide to mono(cyclopentadienyl)hafnium trihalide is between 2 and 10.
바람직한 실시양태에서, 탄화하프늄 세라믹은 상기 기재된 바와 같은 세라믹 전구체 중합체 조성물을 불활성 기체 대기 하에서 약 850℃ 내지 약 950℃의 온도로 가열하여 얻는다. 바람직한 실시양태에서, 세라믹 전구체 중합체는 하기를 포함한다:In a preferred embodiment, the hafnium carbide ceramic is obtained by heating a ceramic precursor polymer composition as described above to a temperature of about 850° C. to about 950° C. under an inert gas atmosphere. In a preferred embodiment, the ceramic precursor polymer comprises:
또 다른 바람직한 실시양태에서, 세라믹 전구체 중합체는 하기를 포함한다:In another preferred embodiment, the ceramic precursor polymer comprises:
바람직한 실시양태에서, x/y 비는 2 내지 10이다.In a preferred embodiment, the x/y ratio is between 2 and 10.
일부 실시양태에서, 세라믹 전구체 중합체 조성물은 하기를 포함한다:In some embodiments, the ceramic precursor polymer composition comprises:
상기 식에서, M은 Hf, Zr, Ti, V, Nb, Ta, W 및 그의 조합으로 이루어진 군으로부터 선택된 금속이며, x 및 y는 0 초과의 정수이다.wherein M is a metal selected from the group consisting of Hf, Zr, Ti, V, Nb, Ta, W and combinations thereof, and x and y are integers greater than zero.
바람직한 실시양태에서, 세라믹 전구체 중합체 조성물에서의 금속은 하프늄이며, 세라믹 전구체 중합체는 하기를 포함한다:In a preferred embodiment, the metal in the ceramic precursor polymer composition is hafnium and the ceramic precursor polymer comprises:
상기 식에서, x 및 y는 0 초과의 정수이다.In the above formula, x and y are integers greater than zero.
일부 실시양태에서, 세라믹 전구체 중합체에서 x/y의 비는 5:1 내지 1:5이다. 바람직한 실시양태에서, x/y의 비는 2:1 내지 1:2이다.In some embodiments, the ratio of x/y in the ceramic precursor polymer is from 5:1 to 1:5. In a preferred embodiment, the ratio of x/y is between 2:1 and 1:2.
일부 실시양태에서, 세라믹 전구체 중합체는 하기 반응에 의하여 염화하프늄 및 2-부틴-1,4-디올로부터 합성된다:In some embodiments, the ceramic precursor polymer is synthesized from hafnium chloride and 2-butyne-1,4-diol by the reaction:
한 실시양태에서, 옥시탄화하프늄 세라믹은 세라믹 전구체 중합체를 불활성 기체 대기 하에서 약 850℃ 내지 약 1,000℃의 온도로 가열하여 얻는다.In one embodiment, the hafnium oxycarbide ceramic is obtained by heating a ceramic precursor polymer to a temperature of about 850° C. to about 1,000° C. under an inert gas atmosphere.
한 실시양태에서, 탄화하프늄 세라믹은 세라믹 전구체 중합체를 불활성 대기 하에서 약 1,000℃ 내지 약 1,600℃의 온도로 가열하여 얻는다.In one embodiment, the hafnium carbide ceramic is obtained by heating a ceramic precursor polymer under an inert atmosphere to a temperature of about 1,000° C. to about 1,600° C.
정의Justice
본 명세서 및 첨부된 청구범위에서 사용된 바와 같이, 하기 용어는 문맥이 달리 요구하지 않는다면 제시된 의미를 가져야 한다.As used in this specification and the appended claims, the following terms shall have the meanings given unless the context requires otherwise.
본원에서 C5H5 또는 대안적으로 Cp에 의하여 나타낸 "시클로펜타디에닐" 리간드는 중첩되는 금속 d-오비탈 및 시클로펜타디에닐 π 전자에 의하여 금속 원자로의 리간드로서 배위결합될 수 있는 평면 오각형, 단일 음하전된 방향족 모이어티이다.A “cyclopentadienyl” ligand, referred to herein by C 5 H 5 or alternatively Cp, is a planar pentagon that can be coordinated as a ligand to a metal atom by overlapping metal d-orbitals and cyclopentadienyl π electrons; It is a single negatively charged aromatic moiety.
"메탈로센"은 금속 중심에 결합되며, 이를 "개재하는" 2개의 시클로펜타디에닐 음이온으로 이루어진 금속 배위결합 착체이다.A "metallocene" is a metal coordination complex consisting of two cyclopentadienyl anions bonded to and "intervening" a metal center.
"하프노센"은 2개의 시클로펜타디에닐 음이온을 배위결합하는 금속이 하프늄인 메탈로센이다."Hafnocenes" are metallocenes in which the metal coordinating the two cyclopentadienyl anions is hafnium.
"폴리(카르보메탈로센)" 중합체는 백본에 혼입된 메탈로센 기를 갖는 중합체이다.A "poly(carbometallocene)" polymer is a polymer having metallocene groups incorporated into the backbone.
"폴리(카르보하프노센)" 중합체는 백본에 혼입된 하프노센 기를 갖는 중합체이다.A "poly(carbohafnocene)" polymer is a polymer having hafnocene groups incorporated into the backbone.
조성물composition
본 발명의 실시양태는 고온 세라믹의 제조를 위한 전구체로서 유용한 금속 함유 중합체의 조성물을 포함한다. 일부 실시양태에서, 그러한 금속 함유 중합체는 폴리(카르보메탈로센) 중합체이다. 일부 실시양태에서, 이러한 폴리(카르보메탈로센) 중합체는 하기 선형 구조를 갖는다:Embodiments of the present invention include compositions of metal containing polymers useful as precursors for the manufacture of high temperature ceramics. In some embodiments, such metal-containing polymers are poly(carbometallocene) polymers. In some embodiments, these poly(carbometallocene) polymers have the following linear structure:
상기 식에서, C5H5는 시클로펜타디에닐 리간드이며, n은 0 초과의 정수이며, M은 Hf, Zr, Ti, V, Nb, Ta 및 그의 조합으로 이루어진 군으로부터 선택된 금속이다. 바람직한 실시양태에서, 금속은 Hf, Zr, Ti 및 그의 조합으로 이루어진 군으로부터 선택된다.wherein C 5 H 5 is a cyclopentadienyl ligand, n is an integer greater than 0, and M is a metal selected from the group consisting of Hf, Zr, Ti, V, Nb, Ta, and combinations thereof. In a preferred embodiment, the metal is selected from the group consisting of Hf, Zr, Ti and combinations thereof.
바람직한 실시양태에서, 금속은 하프늄이다:In a preferred embodiment, the metal is hafnium:
바람직한 실시양태에서, 탄화수소 쇄는 부틸 기이다(구조식 I). 바람직한 실시양태에서, 금속은 하프늄이며, 탄화수소 기는 부틸 기이다(구조식 III).In a preferred embodiment, the hydrocarbon chain is a butyl group (structure I). In a preferred embodiment, the metal is hafnium and the hydrocarbon group is a butyl group (structure III).
일부 실시양태에서, 폴리(카르보메탈로센) 중합체는 분지형 구조를 가지며, 하기와 같이 나타낼 수 있다:In some embodiments, the poly(carbometallocene) polymer has a branched structure and can be represented as:
상기 구조식에서, C5H5는 시클로펜타디에닐 리간드이며, x 및 y는 0 초과의 정수이며, M은 Hf, Zr, Ti, V, Nb, Ta 및 그의 조합으로 이루어진 군으로부터 선택된 금속이다. 바람직한 실시양태에서, 금속은 Hf, Zr, Ti 및 그의 조합으로 이루어진 군으로부터 선택된다. x 대괄호 안에 있는 단량체는 중합체 백본과 함께 선형 폴리(카르보메탈로센)을 제공하며, y 대괄호 안에 있는 단량체는 백본을 따라 연장되며 중합체 백본으로부터 분지되는 반복 폴리(카르보메탈로센) 기를 갖는 분지형 구조이다. 이들 구조에서, x 및 y 지수는 단지 각각 비분지형 및 분지형 단량체의 개수를 지칭하며, 백본을 따라 단량체의 분포의 표시를 제공하지 않아서 랜덤 및 블록 공중합체 둘 다를 아우른다.In the above structural formula, C 5 H 5 is a cyclopentadienyl ligand, x and y are integers greater than 0, and M is a metal selected from the group consisting of Hf, Zr, Ti, V, Nb, Ta, and combinations thereof. In a preferred embodiment, the metal is selected from the group consisting of Hf, Zr, Ti and combinations thereof. The monomers in square brackets x give a linear poly(carbometallocene) with the polymer backbone, and the monomers in square brackets y have repeating poly(carbometallocene) groups extending along the backbone and branching from the polymer backbone. It is a branched structure. In these structures, the x and y indices merely refer to the number of unbranched and branched monomers, respectively, and do not provide any indication of the distribution of monomers along the backbone, encompassing both random and block copolymers.
바람직한 실시양태에서, 금속은 하프늄이다:In a preferred embodiment, the metal is hafnium:
바람직한 실시양태에서, 탄화수소 쇄는 부틸 기이다(구조식 V). 바람직한 실시양태에서, 금속은 하프늄이며, 탄화수소기는 부틸기이다(구조식 VII). 바람직한 실시양태에서, x/y 비는 2 내지 20이다.In a preferred embodiment, the hydrocarbon chain is a butyl group (structure V). In a preferred embodiment, the metal is hafnium and the hydrocarbon group is a butyl group (structure VII). In a preferred embodiment, the x/y ratio is between 2 and 20.
한 실시양태에서, 금속 탄화물 세라믹은 구조식 (I) 내지 (VII) 중 임의의 것을 갖는 폴리(카르보메탈로센) 중합체를 불활성 기체 대기 하에서 가열하여 얻는다. 한 실시양태에서, 불활성 기체는 아르곤이다. 바람직한 실시양태에서, 금속 탄화물 세라믹은 중합체 (III), (IV), (VII) 및 (VIII)로 이루어진 군으로부터 선택된 폴리(카르보하프노센) 중합체를 불활성 기체 대기 하에서 약 850℃ 내지 약 950℃의 온도로 가열하여 형성된 탄화하프늄 세라믹이다.In one embodiment, the metal carbide ceramic is obtained by heating a poly(carbometallocene) polymer having any of structures (I) to (VII) under an inert gas atmosphere. In one embodiment, the inert gas is argon. In a preferred embodiment, the metal carbide ceramic is a poly(carbohafnocene) polymer selected from the group consisting of polymers (III), (IV), (VII) and (VIII) at about 850° C. to about 950° C. under an inert gas atmosphere. It is a hafnium carbide ceramic formed by heating to a temperature of
일부 실시양태에서, 고온 세라믹의 제조를 위한 전구체로서 유용한 금속 함유 중합체 조성물은 탄소열 환원의 공정에 의하여 하프늄 및 탄소의 1:1 화학량론적 비로 탄화하프늄을 형성하는데 사용될 수 있는 산소 함유 하프늄 중합체를 포함한다. 그러한 탄소열 환원에 대한 바람직한 중합체 구조는 하기이다:In some embodiments, a metal-containing polymer composition useful as a precursor for the production of high-temperature ceramics includes an oxygen-containing hafnium polymer that can be used to form hafnium carbide in a 1:1 stoichiometric ratio of hafnium and carbon by the process of carbothermal reduction. do. A preferred polymer structure for such carbothermal reduction is:
상기 구조에서, x 대 y의 비는 5:1 내지 1:5 사이에서 변동될 수 있으며, 바람직한 비는 2:1 내지 1:2이며, 특히 바람직한 비는 1:1이다.In the above structure, the ratio of x to y can vary between 5:1 and 1:5, a preferred ratio is 2:1 to 1:2, and a particularly preferred ratio is 1:1.
200℃ 미만의 온도에서 열적 경화를 수행하여 탄소-탄소 삼중 결합의 중합을 초래하며, 옥시탄화하프늄은 약 850℃ 내지 약 1,000℃의 온도에서 아르곤 하에서 약 80%의 수율로 형성될 수 있다. 아르곤 하에서 1,000℃ 내지 1,600℃의 온도에서 과잉의 탄소 및 산소는 탄소열 환원에 의하여 제거되어 1:1의 Hf 대 C의 화학량론에서 HfC를 형성할 수 있다.Thermal curing is carried out at temperatures below 200° C. resulting in polymerization of carbon-carbon triple bonds, and hafnium oxycarbide can be formed in about 80% yield under argon at temperatures from about 850° C. to about 1,000° C. At temperatures between 1,000° C. and 1,600° C. under argon, excess carbon and oxygen can be removed by carbothermal reduction to form HfC at a stoichiometry of 1:1 Hf to C.
합성 방법synthesis method
바람직한 실시양태에서, 선형 폴리(카르보하프노센) 중합체는 비스(시클로펜타디에닐)하프늄 디할라이드(Cp2HfX2)와 디-그리나드 시약 XMg(CH2)jMgX의 반응에 의하여 합성되며, 여기서 j는 4 또는 5인 정수이다. 바람직한 실시양태에서, 주쇄를 따라 부틸 기를 갖는 폴리(카르보하프노센) 중합체는 하기 반응식 (1)에 의하여 비양성자성 용매 중에서 합성될 수 있다:In a preferred embodiment, the linear poly(carbohafnocene) polymer is synthesized by the reaction of bis(cyclopentadienyl)hafnium dihalide (Cp 2 HfX 2 ) with the di-Grinard reagent XMg(CH 2 ) j MgX , where j is an integer equal to 4 or 5. In a preferred embodiment, poly(carbohapnocene) polymers having butyl groups along the backbone can be synthesized in an aprotic solvent by the following reaction scheme (1):
바람직한 실시양태에서, 반응은 테트라히드로푸란(THF) 중의 ClMgCH2CH2CH2CH2MgCl을 톨루엔 중의 비스(시클로펜타디에닐)하프늄 디클로라이드(Cp2HfCl2)와 혼합하여 수행된다.In a preferred embodiment, the reaction is carried out by mixing ClMgCH 2 CH 2 CH 2 CH 2 MgCl in tetrahydrofuran (THF) with bis(cyclopentadienyl)hafnium dichloride (Cp 2 HfCl 2 ) in toluene.
또 다른 실시양태에서, 백본을 따라 펜틸 기를 갖는 폴리(카르보하프노센) 중합체는 ClMgCH2CH2CH2CH2CH2MgCl과 Cp2HfCl2의 반응에 의하여 합성된다.In another embodiment, a poly(carbohapnocene) polymer having pentyl groups along the backbone is synthesized by the reaction of ClMgCH 2 CH 2 CH 2 CH 2 CH 2 MgCl with Cp 2 HfCl 2 .
바람직한 실시양태에서, 분지형 폴리(카르보하프노센) 중합체는 비스(시클로펜타디에닐)하프늄 디할라이드(Cp2HfX2) 및 모노(시클로펜타디에닐)하프늄 트리할라이드의 혼합물을 디-그리나드 시약 XMg(CH2)jMgX와 반응시켜 합성되며, 여기서 j는 4 또는 5인 정수이다. 바람직한 실시양태에서, 주쇄 및 측쇄를 따라 부틸 기를 갖는 폴리(카르보하프노센) 중합체는 비양성자성 용매 중에서 하기 반응식 (2)에 의하여 합성될 수 있다:In a preferred embodiment, the branched poly(carbohapnocene) polymer is a di-grignard mixture of bis(cyclopentadienyl)hafnium dihalide (Cp 2 HfX 2 ) and mono(cyclopentadienyl)hafnium trihalide. It is synthesized by reacting with reagent XMg(CH 2 ) j MgX, where j is an integer equal to 4 or 5. In a preferred embodiment, poly(carbohalfnocene) polymers having butyl groups along the backbone and side chains can be synthesized by Scheme (2) below in an aprotic solvent:
바람직한 실시양태에서, 반응은 테트라히드로푸란(THF) 중의 ClMgCH2CH2CH2CH2MgCl을 톨루엔 중의 비스(시클로펜타디에닐)하프늄 디클로라이드(Cp2HfCl2) 및 모노(시클로펜타디에닐)하프늄 트리클로라이드(CpHfCl3)와 혼합하여 수행된다.In a preferred embodiment, the reaction is the reaction of ClMgCH 2 CH 2 CH 2 CH 2 MgCl in tetrahydrofuran (THF) with bis(cyclopentadienyl)hafnium dichloride (Cp 2 HfCl 2 ) and mono(cyclopentadienyl) in toluene. It is performed by mixing with hafnium trichloride (CpHfCl 3 ).
또 다른 실시양태에서, 백본 및 측쇄를 따라 펜틸 기를 갖는 폴리(카르보하프노센) 중합체는 Cp2HfCl2 및 CpHfCl3을 ClMgCH2CH2CH2CH2CH2MgCl과 반응시켜 합성된다.In another embodiment, a poly(carbohapnocene) polymer having pentyl groups along the backbone and side chains is synthesized by reacting Cp 2 HfCl 2 and CpHfCl 3 with ClMgCH 2 CH 2 CH 2 CH 2 CH 2 MgCl.
일부 실시양태에서, 반응식 (1) 및 (2) 중 어느 하나에 의하여 형성된 중합체를 불활성 기체 대기 하에서 약 850℃ 내지 약 950℃의 온도로 가열하여 탄화하프늄 세라믹을 형성한다.In some embodiments, a polymer formed by any one of Schemes (1) and (2) is heated under an inert gas atmosphere to a temperature of about 850° C. to about 950° C. to form a hafnium carbide ceramic.
일부 실시양태에서, HfC을 하프늄 대 탄소의 1:1 화학량론으로 형성하기에 적절한 산소 함유 하프늄 중합체는 하기 반응에 의하여 염화하프늄 및 2-부틴-1,4-디올로부터 합성된다.In some embodiments, an oxygen-containing hafnium polymer suitable for forming HfC with a 1:1 stoichiometry of hafnium to carbon is synthesized from hafnium chloride and 2-butyne-1,4-diol by the reaction:
일부 실시양태에서, 상기 전구체는 200℃ 미만의 온도에서 탄소-탄소 삼중 결합의 중합에 의하여 열적 경화된다. 일부 실시양태에서, 열적 경화된 전구체는 아르곤 하에서 약 350℃ 내지 약 1,000℃의 온도에서 가열하여 옥시탄화하프늄을 형성한다. 일부 실시양태에서, 열적 경화된 전구체를 1,000℃ 내지 1,600℃의 온도로 가열하여 탄소열 환원에 의하여 과잉의 탄소 및 산소를 제거하여 1:1 Hf 대 C의 화학량론에서 HfC를 형성한다.In some embodiments, the precursor is thermally cured by polymerization of carbon-carbon triple bonds at a temperature of less than 200°C. In some embodiments, the thermally cured precursor is heated under argon at a temperature of about 350° C. to about 1,000° C. to form hafnium oxycarbide. In some embodiments, the thermally cured precursor is heated to a temperature of 1,000° C. to 1,600° C. to remove excess carbon and oxygen by carbothermal reduction to form HfC at a stoichiometry of 1:1 Hf to C.
실시예Example
실시예Example 1 One
물 응축기, 온도계 및 적하 깔때기가 장착된 500 ㎖ 3목 둥근 바닥 플라스크에 15.19 g(0.04 mol)의 비스(시클로펜타디에닐)하프늄 디클로라이드를 80 g의 톨루엔과 혼합하였다. 수분 오염을 방지하기 위하여 플라스크를 질소 대기 하에서 유지하고, 얼음/소금/물 배쓰에 의하여 외부에서 냉각시켰다. 자기 교반을 사용하여 용액을 진탕시켰다. 용액의 온도가 0℃ 미만이 되면, 30 ㎖의 THF 중의 0.04 몰의 ClMgCH2CH2CH2CH2MgCl 디-그리나드 시약을 적하 깔때기를 통하여 첨가하였다. 반응의 온도는 디-그리나드 시약의 첨가 동안 0℃ 미만에서 유지하였다. 디-그리나드 시약을 약 30 분의 기간에 걸쳐 서서히 첨가하였다. 디-그리나드 시약의 첨가 후, 반응 혼합물을 냉각 배쓰 내에서 2 시간 동안 유지한 후, 냉각 배쓰로부터 꺼내고, 실온에서 밤새 교반하였다. 일부 고체 침전을 갖는 갈색 용액을 얻었다. 액체를 질소 하에서 여과하고, 고체를 20 ㎖의 톨루엔으로 세정하였다. 또한 세정 톨루엔(washing toluene)을 여과하고, 1차 여과액과 합하였다. 그 후, 합한 용액을 감압 하에서 증류시켜 사용된 THF 및 톨루엔 용매를 제거하였다. 단독중합체(III)에 해당하는 13.3 g(이론치 수율의 91%)의 갈색 고체를 얻었다. 900℃로의 아르곤 하에서 얻은 고체의 열중량 분석(TGA)은 69% 수율의 검정 세라믹 잔류물을 제공하였다.Into a 500 ml three neck round bottom flask equipped with a water condenser, thermometer and dropping funnel, 15.19 g (0.04 mol) of bis(cyclopentadienyl)hafnium dichloride was mixed with 80 g of toluene. The flask was kept under a nitrogen atmosphere to prevent moisture contamination and cooled externally by an ice/salt/water bath. The solution was agitated using magnetic stirring. When the temperature of the solution was below 0° C., 0.04 mol of ClMgCH 2 CH 2 CH 2 CH 2 MgCl di-Grinard reagent in 30 mL of THF was added via dropping funnel. The temperature of the reaction was maintained below 0° C. during the addition of the Di-Grignard reagent. Di-Grenard reagent was added slowly over a period of about 30 minutes. After addition of the Di-Grenard reagent, the reaction mixture was kept in a cooling bath for 2 hours, then removed from the cooling bath and stirred overnight at room temperature. A brown solution was obtained with some solid precipitate. The liquid was filtered under nitrogen and the solid was washed with 20 ml of toluene. Washing toluene was also filtered and combined with the primary filtrate. Then, the combined solution was distilled under reduced pressure to remove the used THF and toluene solvents. 13.3 g (91% of theoretical yield) of a brown solid were obtained, corresponding to homopolymer (III). Thermogravimetric analysis (TGA) of the solid obtained under argon to 900° C. gave a black ceramic residue in 69% yield.
실시예Example 2 2
물 응축기, 온도계 및 적하 깔때기가 장착된 500 ㎖ 3목 둥근 바닥 플라스크에 15.19 g(0.04 mol)의 비스(시클로펜타디에닐)하프늄 디클로라이드 및 3.5 g(0.01 mol)의 (시클로펜타디에닐)하프늄 트리클로라이드를 100 g의 톨루엔과 혼합하였다. 수분 오염을 방지하기 위하여 플라스크를 질소 대기 하에서 유지하고, 얼음/소금/물 배쓰에 의하여 외부에서 냉각시켰다. 자기 교반을 사용하여 용액을 진탕시켰다. 용액의 온도가 0℃ 미만이 되면, 40 ㎖의 THF 중의 0.055 몰의 ClMgCH2CH2CH2CH2MgCl 디-그리나드 시약을 적하 깔때기를 통하여 첨가하였다. 반응의 온도는 디-그리나드 시약의 첨가 동안 0℃ 미만에서 유지하였다. 디-그리나드 시약을 약 30 분의 기간에 걸쳐 서서히 첨가하였다. 디-그리나드 시약의 첨가 후, 반응 혼합물을 냉각 배쓰 내에서 2 시간 동안 유지한 후, 냉각 배쓰로부터 꺼내고, 실온에서 밤새 교반하였다. 일부 고체 침전을 갖는 갈색 용액을 얻었다. 액체를 질소 하에서 여과하고, 고체를 25 ㎖의 톨루엔으로 세정하였다. 세정 톨루엔도 또한 여과하고, 1차 여과액과 합하였다. 그 후, 합한 용액을 감압 하에서 증류시켜 사용된 THF 및 톨루엔 용매를 제거하고, 공중합체 (VII)에 해당하는 16.5 g(이론치 수율의 90%)의 암갈색 고체를 얻었다. 900℃로의 아르곤 하에서 얻은 TGA는 65% 수율의 검정 세라믹 잔류물을 제공하였다.To a 500 mL three-necked round bottom flask equipped with a water condenser, thermometer and dropping funnel were added 15.19 g (0.04 mol) of bis(cyclopentadienyl)hafnium dichloride and 3.5 g (0.01 mol) of (cyclopentadienyl)hafnium. Trichloride was mixed with 100 g of toluene. The flask was kept under a nitrogen atmosphere to prevent moisture contamination and cooled externally by an ice/salt/water bath. The solution was agitated using magnetic stirring. When the temperature of the solution reached below 0° C., 0.055 moles of ClMgCH 2 CH 2 CH 2 CH 2 MgCl di-Grinard reagent in 40 mL of THF was added via dropping funnel. The temperature of the reaction was maintained below 0° C. during the addition of the Di-Grignard reagent. Di-Grenard reagent was added slowly over a period of about 30 minutes. After addition of the Di-Grenard reagent, the reaction mixture was kept in a cooling bath for 2 hours, then removed from the cooling bath and stirred overnight at room temperature. A brown solution was obtained with some solid precipitate. The liquid was filtered under nitrogen and the solid was washed with 25 ml of toluene. Wash toluene was also filtered and combined with the first filtrate. The combined solution was then distilled under reduced pressure to remove the THF and toluene solvents used, and 16.5 g (90% of theoretical yield) of a dark brown solid corresponding to copolymer (VII) was obtained. TGA obtained under argon to 900° C. gave a black ceramic residue in 65% yield.
실시예Example 3 3
물 응축기 및 온도계가 장착된 250 ㎖ 3목 둥근 바닥 플라스크에 70 g의 증류수를 첨가하였다. 플라스크를 자기 교반하고, 얼음/물로 외부에서 냉각시킨 후, 30 g의 염화하프늄을 여러 부분으로 나누어 첨가하였다. 실온으로 냉각시킨 후, 12.1 g의 2-부틴-1,4-디올을 첨가하였다. 이 때, 용액을 침전 없이 2종의 성분으로 포화시켰다. 그 후, 상기 용액을 250 ㎖ 비이커에 옮기고, 핫 플레이트 상에서 150-200℃로 가열하였다. 물 및 HCl이 가열 동안 용액으로부터 방출되었다. 용액은 갈색으로 변색되었으며, 점도는 점진적으로 증가되었다. 히드록실 기의 축합 및 탄소-탄소 삼중 결합의 부분 중합이 가열 동안 발생하였다. 모든 물이 증발된 후, 암갈색을 갖는 29 g의 조밀한 고체를 얻었다. 900℃로의 아르곤 하에서 얻은 고체의 TGA는 80% 수율의 검정 세라믹 잔류물을 제공하였다. 1,600℃로의 추가의 가열은 화학량론 HfC를 산출하였다.70 g of distilled water was added to a 250 ml 3 neck round bottom flask equipped with a water condenser and thermometer. After the flask was magnetically stirred and cooled externally with ice/water, 30 g of hafnium chloride was added in portions. After cooling to room temperature, 12.1 g of 2-butyne-1,4-diol were added. At this time, the solution was saturated with both components without precipitation. The solution was then transferred to a 250 ml beaker and heated to 150-200 °C on a hot plate. Water and HCl were released from the solution during heating. The solution turned brown and the viscosity increased gradually. Condensation of hydroxyl groups and partial polymerization of carbon-carbon triple bonds occurred during heating. After all the water evaporated, 29 g of a dense solid with a dark brown color was obtained. TGA of the obtained solids under argon to 900° C. gave an 80% yield of a black ceramic residue. Further heating to 1,600 °C yielded the stoichiometry HfC.
상기 기재된 본 발명의 실시양태는 단지 예시를 위하여 제공하며, 다양한 수정예 및 변형예는 해당 기술분야의 기술자에게 자명할 것이다. 상기 모든 수정예 및 변형예는 첨부하는 청구범위에서 정의된 바와 같이 본 발명의 범주 내에 포함하고자 한다.The embodiments of the present invention described above are provided for illustrative purposes only, and various modifications and variations will be apparent to those skilled in the art. All such modifications and variations are intended to fall within the scope of this invention as defined in the appended claims.
Claims (22)
여기서, C5H5는 시클로펜타디에닐 리간드이며, n, x 및 y는 0 초과의 정수이며, M은 Hf, Zr, Ti, V, Nb, Ta 및 그의 조합으로 이루어진 군으로부터 선택된 금속이다.A ceramic precursor polymer composition comprising at least one poly(carbometallocene) selected from the group consisting of:
wherein C 5 H 5 is a cyclopentadienyl ligand, n, x and y are integers greater than 0, and M is a metal selected from the group consisting of Hf, Zr, Ti, V, Nb, Ta and combinations thereof.
여기서, C5H5는 시클로펜타디에닐 리간드이며, X1 및 X2는 할라이드이며, n은 0 초과의 정수이다.The ceramic precursor polymer composition according to claim 3, which is synthesized by a Grignard coupling reaction according to the following reaction:
wherein C 5 H 5 is a cyclopentadienyl ligand, X 1 and X 2 are halides, and n is an integer greater than zero.
상기 식에서, C5H5는 시클로펜타디에닐 리간드이며, X1, X2 및 X3은 클로라이드 및 브로마이드로 이루어진 군으로부터 각각 선택된 할라이드이며, x 및 y는 0 초과의 정수이다.The ceramic precursor polymer composition according to claim 5, synthesized by a Grignard coupling reaction of bis(cyclopentadienyl)hafnium dihalide and mono(cyclopentadienyl)hafnium trihalide according to the following reaction formula:
In the above formula, C 5 H 5 is a cyclopentadienyl ligand, X 1 , X 2 and X 3 are each a halide selected from the group consisting of chloride and bromide, and x and y are integers greater than zero.
비스(시클로펜타디에닐)하프늄 디할라이드를 화학식 XMg(CH2)jMgX의 디-그리나드 시약과 반응시키는 단계를 포함하며, 여기서 X가 할라이드이며, j가 4 또는 5인 폴리(카르보하프노센) 중합체의 형성 방법.providing bis(cyclopentadienyl)hafnium dihalide; and
reacting bis(cyclopentadienyl)hafnium dihalide with a di-grignard reagent of the formula XMg(CH 2 ) j MgX, wherein X is a halide and j is 4 or 5; Nosen) Methods of Forming Polymers.
여기서, M은 Hf, Zr, Ti, Nb, Ta, W 및 그의 조합으로 이루어진 군으로부터 선택된 금속이며, x 및 y는 0 초과의 정수이다.A ceramic precursor polymer composition comprising:
wherein M is a metal selected from the group consisting of Hf, Zr, Ti, Nb, Ta, W, and combinations thereof, and x and y are integers greater than zero.
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